Azo dyestuffs



Patented Dec. 17, 1940 UNITED STATES AZO DYESTUFFS Richard Fleischhauer and Ernst Korten, Frankfort-on-the-Main-Fechenheim, Germany, assignors to General Aniline & Film Corporation, a corporation of Delaware No Drawing. Application January 80, 1939, Se-

rial No. 253,608. In Germany January 25,

6 Claims.

The "present invention relates to azo dyestuffs.

We have found thatcompounds of the following general formula:

NR1-N=NRi wherein R1 represents an aryl group of the benzeneseries, R2 represents a member of the group consisting of aryl of the benzene series, aralkyl of the benzene series, cycloalkyl and alkyl containing less than ten carbon atoms, R3 represents the radical of a carboxylic acid of the formula -CO-X wherein X represents a member of the group consisting of alkyl, -alkyl-cycloalkyl and cycloalkyl, the sum of the carbon atoms in the carboxylic acid radical amounting to at least siX, the sum of the carbon atoms in the radicals R2 and R3 amounting to at least twelve, R4 represents the radical of a coupling component of the group consisting of pyrazolone-l-aryl-sulfonic acids, aryl being of the benzene series, and 1- acylamino 8 hydroxy-naphthalene-disulfonic acids, are new valuable azo dyestuffs which are especially suitable for dyeing wool or silk. They are obtainable by combining a pyrazolone-sulfonic acid or a peri-acylaminohydroxy-naphthalene-disulfonic acid with a diazo compound of an aromatic amine having the following general formula:

wherein the free amino group may stand in ortho-, metaor para-position to the substituted amino group, and wherein X1 stands for a member of the group consisting of aryl, aralkyl or cycloalkyl and alkyl containing less than ten carbon atoms, and X2 represents the radical of a carboxylic acid of the formula CO--Y wherein Y represents a member of the group consisting of alkyl, -alkyl-cycloalkyl and cycloalkyl, the sum of the carbon atoms in the carboxylic acid radical amounting to at least six, the sum of the carbon atoms contained in X1 and X2 amounting to at least twelve, and wherein the benzene nucleus may contain further substituents, such as methyl, methoxy or chlorine.

The dyeings produced by means of these dyestufls are distinguished by a very good fastness to Washing, fulling and to sea-water and a good fastness to perspiration and to light; furthermore, they display the valuable property of having an especially good affinity for animal fibers when applied in a neutral bath, the dyeing bath being, in most cases, nearly completely exhausted.

As is known, this property .is of practical importance for certain purposes, in particular for dyeing mixed threads and fabrics made from vegetable and animal fibers. The present process is, therefore, of special technical advantage.

The diazo components used for the present process may be obtained according to known methods, for instance, by causing an aliphatic or cycloaliphatic carboXylic acid chloride containing at least six carbon atoms to act upon a nitroami-no-benzene substituted in the amine group by an aromatic or cycle-aliphatic radical or by an aliphatic radical with less than ten carbon atoms, and reducing the nitro compound thus obtained. It is also possible to cause the above-named carboxylic acid chloride to react with an alkylor cycloalkylaminobenzene, then nitrating the acyl derivative thus obtained and reducing the nitro compound formed.

For the present process, it is essential that the acyl radical is of aliphatic or cycloaliphatic nature and contains at least 6 carbon atoms. For it has been ascertained that these radicals surprisingly impart to the dyestuifs a better dyeing power, in a neutral bath, than do aromatic radicals containing the same number of carbon atoms. Thus, the dyestufi described in Example 1 of the present invention, for instance, dyes considerably better, in a neutral bath, than does the corre sponding dyestuff containing a phenylacetyl group in the diazo component.

The radicals of the following acids may be named as examples: cyclohexyl-acetic acid, cycloheXyl-propionic acid, hexanoic acid, isoheptanoic acid, n-octanoic acid, capric acid, lauric acid, palmitic acid, stearic acid, and mixtures of such acids obtained by technical processes.

The carbon chains of the acids may also be interrupted by oxygen atoms, such as is, for instance, the case with the isoheptyl-oXy-acetic acid of the formula: H15C7OCH2COOH.

The new azo dyestuffs obtained according to the above-described process are superior to the known dyestuffs having a similar constitution by their better aflinity to the fiber in 'a neutral bath as well as by their better solubility, or by their better fastness to light.

The following examples serve to illustrate th invention but they are not intended to limit it thereto:

1. 31.4 kgs. of 1-amino-4-N-cyclohexyl-cycloheXylacetyl-aminobenzene are diazotized in the usual manner. The diazo-compound obtained is combined with a solution, rendered alkaline with sodium carbonate, of 29 kgs. of 1-(2'-chloro-5'- sulfophenyl)-3-methyl-5-pyrazolone. The dyestuff formed is isolated and dried; it is a greenyellow powder which is soluble in water and dyes wool, in a neutral bath, very fast yellow-greenish tints.

A similar dyestuil having a somewhat enhanced alfinity to the fiber is obtained by using as diazo component 1-amino-4-N-cyclohexyl-cyclohexylpropionyl-aminobenzene.

2. 30.4 kgs. of 1-amino-2-methyl-5-N-ethylcaprinyl-amino-benzene are diazotized and the diazo compound obtained is combined with a solution, alkaline with sodium carbonate, of 26 kgs. of l-(4-sulfophenyl) -3-methyl-5-pyrazolone. The dyestufl is isolated and dried; it then constitutes a water-soluble, yellow-brown powder which dyes wool, in a neutral bath, very fast reddish-yellow tints.

A greenish-yellow having the same good properties, but a somewhat enhanced fastness to light, is obtained if 1-(2'-chloro-6'-methyl-4'-sulfophenyl)-3 -methyl-5pyrazolone is used as azo component. V 3. 33.2 kgs. of a mixtureof amino compounds (obtained by the action of the chlorides of a mixture of fatty acids containing 7-9 carbon atoms upon 1-isoheptylamino-4-nitrobenzene and subsequent reduction of the nitro compounds thus are diazotized. The mixture of diazo compounds thus obtained is combined with a solution, alkaline with sodium carbonate, of 29 kgs. of 1-(2- chloro 5'-sulfophenyl) 3 methyl-5-pyrazolone. The dyestuff is isolated and dried; it is obtained in the form of a water-soluble brown-yellow powder which dyes wool, in a neutral or acid bath, very fast greenish-yellow tints.

1-isoheptylamino-4-nitrobenzene is obtained by condensing 1-chloro-4-nitrobenzene-2-sulfonio acid with isoheptylamine of the following probable formula:

(obtainable by treating with ammonia and hydrogen, under pressure, the corresponding aldehyde containing '7 carbon atoms which is formed as a by-product in the synthesis of methanol) and splitting off the sulfonic acid group.

4. 34.4 kgs. of 1-amino-4-N-cyclohexyl-caprinyl-aminobenzene are diazotized, and the diazo compound obtained is combined with a solution, alkaline with sodium carbonate, of 50 kgs. of 1 -(2'.5'- dichlorobenzoylamino) 8 hydroxynaphthalene-4.6-disulfonic acid. The dyestuff is isolated and dried; it is obtained in the form of a water-soluble red powder and dyes wool, in a neutral bath, brilliant red'tints. The dyeings obtained with this dyestuif display very good fastness properties, they are particularly fast to washing, fulling, perspiration and light.

By combining the same diazo component with equivalent amounts of l-benzoylamino-B-hydroxynaphthalene-4.6-disulfonic acid, l-benzoylamino-8-hydroxynaphthalene-3.fi-disulfonic acid, 1 (2'.5' dichloro benzoylamino) 8 hydroxynaphthalene-3.6-disulfonic acid or 1-(4'-chloro- 2'.5' diniethyl phenyl sulfonyl-amino) -8-hydroxynaphthalene-3.6 disulfonic acid, there are obtained blue-red dyestuffs which dye wool or silk somewhat more bluish red tints of similarly good properties.

If the capric acid radical contained in the diazo component is replaced by the radicals of a mixture of fatty acids containing seven to nine carbon atoms, dyestufis are obtained which on wool yield dyeings having nearly the same tints and similarly good fastness properties as regards fulling and perspiration, and a still somewhat better fastness to light.

5. 34.4 kgs. of 1-amino-4-N-n-butyl-cyclohexylcapronylaminobenzene of the following forare diazotized, and the diazo compound obtained is combined with a solution, alkaline with sodium carbonate, of 26 kgs. of 1-(4'-sulfophenyl) -3- methyl-5-pyrazolone. The product is isolated and dried; it is obtained in the form of a reddishyellow powder which dyes wool, in a neutral bath, fast greenish-yellow tints.

7. 37.2 kgs. of 1-amino-4-N-cyclohexyl-laurylamino-benzene are diazotized, and the diazo compound obtained is combined with a solution, alkaline with sodium carbonate, of 44 kgs. of 1- chloroacetylamino-8-hydroxy-naphthalene 4.6 disulfonic acid. The dyestufi is isolated and dried; it is a red powder which dyes wool, in a neutral bath very'fast vivid red tints.

A somewhat more bluish dyestuif having similar properties is obtained with 1-acetylamino-8- hydroxy-naphthalene-3.6-disulf0nic acid.

Quite similar dyestuffs are obtained, for instance, by using 1-amino-4-N-isoheptyl-caprinylamino-benzene, 1-amino-4-N-ethyl-stearyl-aminobenzene, 1-amino-4-N-isoheptyl-palmityl-aminobenzene and the like.

8. 34.4 kgs. of l-amino-4-N-cyclohexylcaprinyl-aminobenzene are diazotized, and the diazo compound obtained is combined with an aqueous solution of the sodium salt of 50 kgs. of 1-(2-chlorophenoxy-acetylamifno) -8 hydroxy naphthalene-4.fi-disulfonic acid, in the presence of an excess of sodium carbonate.

The dyestuff thus obtained is isolated and dried; it is a red water-soluble powder which dyes wool, in a neutral bath, vivid scarlet tints of very good fastness to washing, perspiration, fulling and over-dyeing andof very good fastness to light.

The following table illustrates a number of fur- Tag-3 6.453

ther dyestufis which may be obtained according to the present invention:

wherein X represents a member of the group consisting of alkyl, -alkyl-cycloalkyl and cycloalkyl,

5 Diaz o component Az o component Shade on wool 1-amino4-N-ethy1-stearyl-aminobenzene. l l-benzoylamino-8-hydroxynaphtha1ene 4.6-disulfonic acid: Bluish red. l-amino-4-N-isopropyl-cyolohexylpropionyl-aminobenzene. l- (2!-chloro-6-methyl-4'-suliophenyl) -3-n1ethyl-5-'pyra- Greenish-yellow.

' zo one. l 1-amino-4-N-n-butyl-cyclohexylpropionyl-aminobenzenc. do Do. l-amino-2-methyl-5-N-ethyl-caprinyl-aminobenzene l- (fflfifW-dichloobenzoylamino) -8-oxyn aphth alene- 4.6 di Bluish-red.

10 l-amino-4-N-is0heptyl-caprinyl-aminobenzene do Do. l-amino-l N-isoheptyl-laurinyl amifiobenzone do; Do. l-amino-i-N-cyclo-hexyl-isooenanthyl-aminebenzene 1-(4-sulfophenyl)-3-methyl-5-pyrazolone Reddish yellow. l-amino-4-N-eyelohexyl-caprinylamino'aminobenzene. l-g2-chloro-6-methyl-4'-sulfophenyl)-3- Greenish yellow.

one 1-amino-4-N'cyclohexyl-[oenanthyl-caprylor pelargonyldo Do.

aminobenzene].

l-amino-4-N-cyclohexyl-caprinyl-aminobenzene 1-(2-chloro-5-sulfophenyl)-3-methy1-5-pyrazolone Do.

' 1-amino-2-N-cyclohexyl-caprinyl-aminobenzene. .do Do. l-amino-4-N-cyclohexyl-caprinyl-aminobenzene 1-(2,5-dichloro-4-sulfophenyl)-3-methyl-5-pyrazolone Do. l-amino-4-N-cyclohexyl-hexahydrobenzoybaminobenzene 1-(2-chloro-5-sulfophenyl)3-n1ethyl-5-pyrazolone Do. l-aminoi-N- cyclohexyl cyclohexylpropionyl aminoben 1- g2 -chloro-6-methyl-4-suliophenyl) -3 methyl 5 pyrazo Do.

one l-(3-sulfophenyl)-3-methyl-5-pyrazolone Reddish yellow. l-(2-sulfophenyl)-3-phenyl-5-pyrazolone Orange-yellow.

1-(2-methyl-4-sulfophenyl)-3-methyl-5-pyrazolo Yellow. 1-(2'-chloro-4'-sulfophenyl)-3-methyl-5-pyrazolone... Greenish yellow. 1-(2.5-dichlorobenzoyl-amino)-8-hydroxy-naphthale Bright bluish red. I disulfonio acid. l-aminoA-N-cyclohexyl-cyclohexyl-capronyl-aminoben 1-gT-chloro-6-methyl-4-su1fophenyl)-3-methyl-5-pyrazo- Greenish yellow.

zene. one.

Do 1-(4-nitrobenzoyl-amino)-8-hydroxynaphthalene-4.B-disul- Bluish red.

fonic acid.

l-amino-4-N-phenyl-caprinyl-aminobenzene 1-(4-suliophenyl)-3-methyl-5-pyrazolone Reddish-yellow. l-amino-Z-methyl-5-N-benzyl-caprinyl-aminobenzene 1-g,Eakdichlorggbenzoylamino)-8-hydroxynaphthalene-Ld Bluish-l'ed.

lSIl omc aci l-amino-3-metl1oxyi-N-benzyl-caprinyl-aminobenzene l-benzoylamino-8-hydroxy-naphthalene4.6-disulfonie acid. Red-violet. l-amino-4-N-benzyl-caprinyl-aminobenzene 1-(2-chloro-5-s11liophenyl)-3-methyl-5-pyrazo1one Greenish yellow.

Do l (4 chloro 2 ,5 dimethylphenylsulionylamino) 8 -oxy Violet-red.

naphthalene-3.6-d1sulfonic-acid.

1amino-2-methyl-5-N-benzyl-caprinyl-aminobenzene 1-(Zi-chloro-6-methyl-4-sulfophenyl)-3-methyl-5 pyra- Greenish yellow.

20 one.

We claim: the sum of the carbon atoms in the carboxylic 1. The compounds of the general formula: acid radical amounting to at least six, the sum of the carbon atoms in the radicals R2 and R3 amounting to at least twelve, R4 represents the radical of a coupling component of the group R3 consisting of pyrazolone-l-aryl-sulfonic acids, wherein R1 represents an aryl group of the benaryl being of the benzene series, and l-acylaminozene series, R2 represents a. member of the group y O yp thale e-li sulfomc acids.

consisting of aryl of the benzene series, aralkyl The Co po s o t general formula; of the benzene series, cycloalkyl and alkyl containing less than ten carbon atoms, R3 represents c 01011 x 1 45 radical of a carboxylic acid of the formula: y e

wherein X represents a member of the group con- R3 sisting of alkyl, -alkyl-cycloalkyl and cycloalkyl,

r t e Sum 0f the Carlwn o s in e carboxylic wherein R2 represents the radical of a carboxylic 00 ac1d radical amounting to at least six, the sum of acid of t formula;

the carbon atoms in the radicals Re and Ra amounting to at least twelve, R4 represents the X radical of a coupling component of the group V consisting of pyrazolone-l-aryl-sulfonic-acids,

aryl being of the benzene series, and lacylaminowherein X represents a member f the group y yp t acldsconsisting of alkyl, -alkyl-cycloalkyl and cycloal- The compounds of the gene! formula: kyl, the sum of the carbon atoms in the carboxylic R: acid radical amounting to at least six, R4 rep- T resents the radical of a coupling component of the group consisting of pyrazolone-l-aryl-sul- R3 ionic acids, aryl being of the benzene series, and

wherein R2 represents a member of the group 1 -acylamino- 8 -hydroxy-naphthalene-disu1fonic consisting of aryl of the benzene series, aralkyl acids.

of the benzene series, cycloalkyl and alkyl con- 4. The compound of the formula:

cyclohexyl OH SOaNa N- N=NC=C l cyclohexylC Hr-C 137-0 0 /N 70 CH3-C=N taining less than ten carbon atoms, R: represents the radical of a carboxylic acid of the formula:

being a watersoluble greenish yellow dyestufi which dyes wool in a neutral bath greenish-yellow tints of very good fastness to washing, fulling and light.

7 5., The compound'of the formula:

0 H N H- C 0 5 cyclohexyl\ Q N-ONCN c1 caprinyl-C 0 6. The compound of the formula:

cyclohexyl N- N: 5 captiny10 0 S O 3N8 SOzNa being a watersoluble bluish red dye stufi which 10 dyes wool in a neutral bath bluish red tints 01? good fastness to washing, fulling and light.

RICHARD FLEISCHHAUER. ERNST KORTEN. 15 

